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Preheat oven to 325°F. Spray 10-inch Bundt pan with nonstick spray.
Whisk together flour, sugar, baking powder, baking soda, and salt in medium bowl. Combine cocoa and chopped chocolate in small bowl. Pour boiling water over cocoa mixture, stirring until chocolate is melted.
Whisk together buttermilk, oil, egg, egg white, and vanilla in large bowl; stir in cocoa mixture. Add flour mixture, stirring just until no longer visible. Stir in chocolate chips. Pour batter into prepared pan.
Bake until toothpick inserted into center of cake comes out clean, 45–50 minutes. Let cool in pan on wire rack 10 minutes. Invert and remove pan. Let cool completely.